CN111620858A - Novel compound and organic electronic device using the same - Google Patents

Novel compound and organic electronic device using the same Download PDF

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CN111620858A
CN111620858A CN202010123332.4A CN202010123332A CN111620858A CN 111620858 A CN111620858 A CN 111620858A CN 202010123332 A CN202010123332 A CN 202010123332A CN 111620858 A CN111620858 A CN 111620858A
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陈济中
谢淑珠
陈政斌
李明哲
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Shanghai Nichem Fine Chemical Co Ltd
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Abstract

The present invention provides a novel compound represented by the following formula (I):
Figure DDA0002393658580000011
wherein, b is connected to either a1 or a2, and c is connected to the other of a1 or a 2; l is1To L2Each independently is an arylene group having 6 to 60 carbon atoms in the ring; y is1Is selected from the group consisting ofThe group consisting of: a hydrogen atom, a deuterium atom, an alkyl group having 1 to 12 carbon atoms, and an aryl group having 6 to 30 carbon atoms in the ring; and m1 to m2 are each independently 0 or 1. Organic electronic devices comprising the novel compounds can have an extended useful life.

Description

Novel compound and organic electronic device using the same
Technical Field
The present invention relates to a novel compound and an organic electronic device using the same, and more particularly, to a novel compound for an electron transport material or a hole blocking material and an organic electronic device using the same.
Background
With the progress of technology, various organic electronic devices made of organic materials, such as Organic Light Emitting Diodes (OLEDs), organic phototransistors (organic phototransistors), organic photovoltaic cells (organic photovoltaic cells), and organic photodetectors, are developed.
OLED was originally invented and proposed by Eastman Kodak, Inc. of Durman Kodak, who deposited an electron-transporting material { e.g., tris (8-hydroxyquinoline) aluminum (III), Alq is abbreviated as Al (8-hydroxyquinoline) aluminum (III) } on a transparent Indium Tin Oxide (ITO) glass formed with an organic aromatic diamine hole-transporting layer by vacuum evaporation (vacuum evaporation method)3]}; and depositing a metal electrode on the electron transmission layer to complete the manufacture of the OLED. The OLED has the advantages of fast response speed, light weight, thinness, wide viewing angle, high brightness, high contrast ratio, no need of a backlight source, and low energy consumption, and thus attracts attention, but the OLED still has the problem of low efficiency.
In order to overcome the problem of low efficiency, one of the improvement ways is to provide an intermediate layer between the cathode and the anode, as shown in fig. 1, the improved OLED device 1 sequentially includes a substrate 11, an anode 12, a hole injection layer 13 (HIL), a hole transport layer 14 (HTL), a light emitting layer 15 (EL), an electron transport layer 16 (ETL), an electron injection layer 17 (EIL), and a cathode 18. When a voltage is applied to the anode 12 and the cathode 18, holes emitted from the anode 12 will pass through the HIL and the HTL and move to the EL, and electrons emitted from the cathode 18 will pass through the EIL and the ETL and move to the EL, so that the holes and the electrons are recombined into excitons (exiton) in the EL layer, and light is generated when the excitons decay from an excited state to a ground state.
Another improvement is to modify the ETL material in an OLED such that the electron transport material exhibits hole blocking capability, and conventional electron transport materials include 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (2,9-dimethyl-4,7-diphenyl-1, 10-phenanthrone, BCP), 3 '- [ 5' - [3- (3-pyridyl) phenyl ] [1,1 ': 3', 1 '-terphenyl ] -3, 3' -diyl ] bipyridine { (3,3 '- [ 5' - [3- (3-pyridinyl) phenyl ] [1,1 ': 3', 1 '-terphenyl ] -3, 3' -diyl ] bipyridine, TmPb }, 1,3,5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene [1,3,5-tris (1-phenyl-1H-benzimidazol-2-yl) bezene, TPBi ], tris (2,4,6-trimethyl-3- (3-pyridyl) phenyl) borane [ tris (2,4,6-trimethyl-3- (pyridine-3-yl) phenyl) borane,3TPYMB ], 1,3-bis (3, 5-bipyridin-3-yl-phenyl) benzene [1,3-bis (3, 5-dipyridin-3-yl-phenyl) bezene, BmPy ] Pb, and 9,10-bis (3- (3-pyridyl) phenyl) anthracene [9,10-bis (3- (pyridine-3-yl) phenyl) anthrene, DPyPA ].
However, even with the use of the electron transport material, there is room for improvement in the lifetime (life span) of the OLED device, and thus, the present invention provides a novel compound to overcome the problems of the prior art.
Disclosure of Invention
It is an object of the present invention to provide a novel compound which is useful for organic electronic devices.
It is another object of the present invention to provide an organic electronic device using the novel compound, thereby extending the lifespan of the organic electronic device.
To achieve the above object, the novel compounds of the present invention are represented by the following formula (I):
Figure BDA0002393658560000021
in formula (I), a1, a2, b, and c represent the connecting positions, b is connected to either a1 or a2, and c is connected to the other of a1 or a 2.
In the formula (I), G1B is
Figure BDA0002393658560000022
In the formula (I), G2Selected from the group consisting of:
Figure BDA0002393658560000023
wherein Z is1And Z2Each independently selected from the group consisting of: a substituted aryl group having 6 to 60 carbon atoms in the ring, an unsubstituted aryl group having 6 to 60 carbon atoms in the ring, a substituted heteroaryl group having 3 to 60 carbon atoms in the ring, and an unsubstituted heteroaryl group having 3 to 60 carbon atoms in the ring.
m1 to m4 are each independently 0 or 1, and m1 to m4 are the same as or different from each other.
L1To L4Each independently an arylene group having 6 to 60 carbon atoms in the ring, and L1To L4The same or different from each other.
Y1To Y3Each independently selected from the group consisting of: hydrogen atom, deuterium atom, alkyl group having 1 to 12 carbon atoms and aryl group having 6 to 30 carbon atoms in the ring, and Y1To Y3The same or different from each other.
Preferably, the compound is represented by any one of the following formulae (I-I) to (I-XVI):
Figure BDA0002393658560000024
Figure BDA0002393658560000031
Figure BDA0002393658560000041
preferably, Z1And Z2Each independently selected from the group consisting of:
Figure BDA0002393658560000042
wherein R is1To R7Each independently selected from the group consisting of: a hydrogen atom, a deuterium atom, a halogen group, a cyano group, a nitro group, a trifluoromethyl group, an unsubstituted alkyl group having 1 to 12 carbon atoms, an unsubstituted alkenyl group having 2 to 12 carbon atoms, an unsubstituted alkynyl group having 2 to 12 carbon atoms, an unsubstituted aryl group having 6 to 30 carbon atoms in the ring, an unsubstituted heteroaryl group having 3 to 30 carbon atoms in the ring, and a heteroaryl group having 3 to 30 carbon atoms in the ring.
Wherein the substituents are selected from the group consisting of: deuterium atom, halogen group, cyano group, nitro group, and trifluoromethyl group.
Wherein m is an integer of 1 to 4, n is an integer of 1 to 3, and o is 1 or 2.
Preferably, Z1Selected from the group consisting of:
Figure BDA0002393658560000051
Figure BDA0002393658560000052
and
Z2selected from the group consisting of:
Figure BDA0002393658560000053
Figure BDA0002393658560000061
wherein R is1To R7Each independently selected from the group consisting of: hydrogen atom, deuterium atom, halogen groupCyano, nitro, trifluoromethyl, an alkyl group which is unsubstituted and has a carbon number of 1 to 12, an alkyl group which is substituted with a substituent and has a carbon number of 1 to 12, an alkenyl group which is unsubstituted and has a carbon number of 2 to 12, an alkenyl group which is substituted with a substituent and has a carbon number of 2 to 12, an alkynyl group which is unsubstituted and has a carbon number of 2 to 12, an aryl group which is unsubstituted and has a carbon number of 6 to 30 on the ring, an aryl group which is substituted with a substituent and has a carbon number of 6 to 30 on the ring, a heteroaryl group which is unsubstituted and has a carbon number of 3 to 30 on the ring, and a heteroaryl group which is substituted with a substituent and has a carbon number of 3 to 30 on the ring.
Wherein the substituents are selected from the group consisting of: deuterium atom, halogen group, cyano group, nitro group, and trifluoromethyl group.
Wherein m is an integer of 1 to 4, n is an integer of 1 to 3, and o is 1 or 2.
More preferably, R is1To R7Each independently selected from the group consisting of: hydrogen atom, deuterium atom, halogen group, cyano group, nitro group, trifluoromethyl group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, phenyl group, naphthyl group, biphenyl group, terphenyl group, and trifluoromethylphenyl group.
More preferably, Z1And Z2Each independently selected from the group consisting of:
Figure BDA0002393658560000062
Figure BDA0002393658560000071
preferably, in said formula (I), G2Selected from the group consisting of:
Figure BDA0002393658560000072
Figure BDA0002393658560000081
Figure BDA0002393658560000091
Figure BDA0002393658560000101
Figure BDA0002393658560000111
Figure BDA0002393658560000121
Figure BDA0002393658560000131
Figure BDA0002393658560000141
Figure BDA0002393658560000151
Figure BDA0002393658560000161
Figure BDA0002393658560000171
Figure BDA0002393658560000181
Figure BDA0002393658560000191
Figure BDA0002393658560000201
Figure BDA0002393658560000211
Figure BDA0002393658560000221
Figure BDA0002393658560000231
more preferably, in said formula (I), G2Selected from the group consisting of:
Figure BDA0002393658560000232
Figure BDA0002393658560000241
preferably, the compound is represented by L1To L4Each arylene group having 6 to 60 carbon atoms in the ring is independently selected from the group consisting of:
Figure BDA0002393658560000242
wherein m is an integer of 1 to 4, n is an integer of 1 to 3, and o is 1 or 2.
Wherein, X1And X2Each independently selected from the group consisting of: a hydrogen atom, a deuterium atom, a halogen group, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 30 carbon atoms in the ring, a heteroaryl group having 3 to 30 carbon atoms in the ring, and an aryloxy group having 6 to 30 carbon atoms in the ring.
Preferably, Y is1To Y3Each independently selected from the group consisting of: hydrogen atom, deuterium atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, phenyl group, biphenyl group, and naphthyl group.
In the specification, L1、L2、L3Or L4The "arylene group having 6 to 60 carbon atoms on the ring" may be an unsubstituted arylene group having 6 to 60 carbon atoms on the ring or an arylene group having 6 to 60 carbon atoms on the ring and substituted with a substituent; the substituent on the arylene group may be the aforementioned X1To X2Any of them.
In the specification, the "alkyl group" may be an unsubstituted alkyl group or an alkyl group substituted with a substituent; the "alkenyl" may be unsubstituted alkenyl or alkenyl substituted with a substituent; the "alkynyl" group may be an unsubstituted alkynyl group or an alkynyl group substituted with a substituent; substituents on the aforementioned alkyl, alkenyl and alkynyl groups can be, but are not limited to, deuterium atoms.
Specifically, the compound is selected from the group consisting of:
Figure BDA0002393658560000251
Figure BDA0002393658560000261
Figure BDA0002393658560000271
Figure BDA0002393658560000281
Figure BDA0002393658560000291
Figure BDA0002393658560000301
Figure BDA0002393658560000311
Figure BDA0002393658560000321
Figure BDA0002393658560000331
Figure BDA0002393658560000341
Figure BDA0002393658560000351
Figure BDA0002393658560000361
Figure BDA0002393658560000371
Figure BDA0002393658560000381
Figure BDA0002393658560000391
Figure BDA0002393658560000401
Figure BDA0002393658560000411
Figure BDA0002393658560000421
Figure BDA0002393658560000431
Figure BDA0002393658560000441
Figure BDA0002393658560000451
Figure BDA0002393658560000461
Figure BDA0002393658560000471
Figure BDA0002393658560000481
Figure BDA0002393658560000491
Figure BDA0002393658560000501
Figure BDA0002393658560000511
Figure BDA0002393658560000521
Figure BDA0002393658560000531
Figure BDA0002393658560000541
Figure BDA0002393658560000551
Figure BDA0002393658560000561
Figure BDA0002393658560000571
Figure BDA0002393658560000581
Figure BDA0002393658560000591
Figure BDA0002393658560000601
Figure BDA0002393658560000611
Figure BDA0002393658560000621
Figure BDA0002393658560000631
Figure BDA0002393658560000641
Figure BDA0002393658560000651
Figure BDA0002393658560000661
Figure BDA0002393658560000671
Figure BDA0002393658560000681
Figure BDA0002393658560000691
Figure BDA0002393658560000701
Figure BDA0002393658560000711
Figure BDA0002393658560000721
Figure BDA0002393658560000731
Figure BDA0002393658560000741
Figure BDA0002393658560000751
Figure BDA0002393658560000761
Figure BDA0002393658560000771
Figure BDA0002393658560000781
Figure BDA0002393658560000791
Figure BDA0002393658560000801
Figure BDA0002393658560000811
Figure BDA0002393658560000821
Figure BDA0002393658560000831
Figure BDA0002393658560000841
Figure BDA0002393658560000851
Figure BDA0002393658560000861
Figure BDA0002393658560000871
Figure BDA0002393658560000881
Figure BDA0002393658560000891
Figure BDA0002393658560000901
Figure BDA0002393658560000911
Figure BDA0002393658560000921
Figure BDA0002393658560000931
Figure BDA0002393658560000941
Figure BDA0002393658560000951
Figure BDA0002393658560000961
Figure BDA0002393658560000971
Figure BDA0002393658560000981
Figure BDA0002393658560000991
Figure BDA0002393658560001001
Figure BDA0002393658560001011
Figure BDA0002393658560001021
Figure BDA0002393658560001031
Figure BDA0002393658560001041
Figure BDA0002393658560001051
Figure BDA0002393658560001061
Figure BDA0002393658560001071
Figure BDA0002393658560001081
Figure BDA0002393658560001091
Figure BDA0002393658560001101
Figure BDA0002393658560001111
Figure BDA0002393658560001121
Figure BDA0002393658560001131
Figure BDA0002393658560001141
Figure BDA0002393658560001151
Figure BDA0002393658560001161
Figure BDA0002393658560001171
Figure BDA0002393658560001181
Figure BDA0002393658560001191
Figure BDA0002393658560001201
Figure BDA0002393658560001211
Figure BDA0002393658560001221
Figure BDA0002393658560001231
Figure BDA0002393658560001241
Figure BDA0002393658560001251
Figure BDA0002393658560001261
Figure BDA0002393658560001271
Figure BDA0002393658560001281
Figure BDA0002393658560001291
Figure BDA0002393658560001301
Figure BDA0002393658560001311
Figure BDA0002393658560001321
Figure BDA0002393658560001331
Figure BDA0002393658560001341
Figure BDA0002393658560001351
Figure BDA0002393658560001361
Figure BDA0002393658560001371
Figure BDA0002393658560001381
Figure BDA0002393658560001391
the present invention also provides an organic electronic device comprising a first electrode, a second electrode and an organic layer disposed between the first electrode and the second electrode, wherein the organic layer comprises the novel compound. The novel compound may be, but is not limited to, any of compounds 1 to 1826.
Preferably, the organic electronic device is an Organic Light Emitting Diode (OLED).
Specifically, the organic light emitting diode comprises a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer; the hole injection layer is formed on the first electrode; the hole transport layer is formed on the hole injection layer; the light-emitting layer is formed on the hole transport layer; the electron transport layer is formed on the light emitting layer; the electron injection layer is formed between the electron transport layer and the second electrode.
In one embodiment, the organic layer can be the electron transport layer, that is, the electron transport layer comprises the novel compounds described above.
For example, the electron transport layer may be a single-layer structure or a multi-layer structure disposed between the light emitting layer and the electron injection layer. When the electron transport layer is a multi-layer structure (e.g., the electron transport layer includes a first electron transport layer and a second electron transport layer), the first electron transport material in the first electron transport layer may include a single one of the above-mentioned novel compounds, and the second electron transport material in the second electron transport layer may include another one of the above-mentioned novel compounds or conventional compounds. Alternatively, the first electron transport material in the first electron transport layer may comprise a combination of one of the above-described novel compounds and another of the above-described novel compounds or a combination of one of the above-described novel compounds and a conventional electron transport material compound, as well as the second electron transport material in the second electron transport layer.
The first and/or second electron transport layers comprise the aforementioned novel compounds (e.g., compounds 1 through 1826). The OLED device using the novel compound as an electron transport material according to the present invention can extend its lifespan as compared to a conventional OLED device using an existing electron transport material such as BCP, TmPyPb, TPBi, 3TPYMB, BmPyPb, or DPyPA.
Preferably, the OLED device further includes a Hole Blocking Layer (HBL) formed between the electron transport layer and the light emitting layer for preventing holes from moving from the light emitting layer to the electron transport layer.
In other embodiments, the organic layer may be the hole blocking layer, that is, the hole blocking layer includes the aforementioned novel compound as a hole blocking material. More preferably, the hole blocking layer comprises the aforementioned novel compounds as compounds 1 to 1826. Compared with the conventional OLED device using the existing hole blocking material such as BCP or 2,3,5, 6-tetramethyl-1-phenyl-1, 4-phthalimide [2,3,5,6-tetramethyl-phenyl-1,4- (bis-thiylimide), TMPP ], the OLED device using the novel compound as the hole blocking material can prolong the service life thereof.
Preferably, the hole injection layer may be a single layer structure or a multi-double layer structure, i.e., the OLED has a first hole injection layer and a second hole injection layer, which are disposed between the first electrode and the hole transport layer.
The first and second hole injection layers may be made of polyaniline (polyaniline), polyethylenedioxythiophene (polyethylenedioxythiophene), 4',4' -Tris (N-3-methylphenyl-N-phenylamino) triphenylamine {4, 4',4' -Tris [ (3-methylphenenyl) phenylamino ] amine]triphenylamine, m-MTDATA }, or N, N '- (4,4' -biphenylyl) bis (N)1- (1-naphthyl)) -N, N' -diphenylbenzene-1, 4-diamine [ N1,N1'-(biphenyl-4,4'-diyl)bis(N1-(naphthalen-1-yl)-N4,N4'-diphenylbenzene-1,4-diamine)]But is not limited thereto.
Preferably, the hole transport layer may also be a double-layer structure, i.e., the OLED device has a first hole transport layer and a second hole transport layer, and the first hole transport layer and the second hole transport layer are disposed between the double-layer hole injection layer and the light emitting layer.
The first and second hole transport layers may be made of 4,4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline]{1,1-bis[(di-4-tolylamino)phenylcyclohexane]TAPC }, carbazole derivatives such as N-phenylcarbazole (carbazole derivative), or N, N '-biphenylyl-N, N' -di (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine [ N4,N4'-di(naphthalen-1-yl)-N4,N4'-diphenylbiphenyl-4,4'-diamine,NPB]But is not limited thereto.
Preferably, the light emitting layer may be made of a light emitting material including a host emitter (host) and a dopant (dopant), wherein the host emitter is made of a material such as 9- [4- (1-naphthyl) phenyl ] -10- (2-naphthyl) anthracene [9- (4- (naphthalene-1-yl) phenyl) -10- (naphthalene-2-yl) anthracene ], but not limited thereto.
For the red OLED, the dopant in the light emitting layer may be a divalent iridium organometallic compound having a quinoline derivative (quinoneitive) ligand or an isoquinoline derivative (isoquinoline derivative) ligand, an osmium complex, or a platinum complex, but is not limited thereto. For the green OLED, the dopant in the light emitting layer may be diaminofluorene (diaminoflourenes), anthracenediamine (diaminoanthracene) or a divalent iridium organometallic compound having a phenylpyridine (phenylpyridine) ligand, but is not limited thereto. For blue-light OLED, the dopant in the light-emitting layer can be amino perylene derivative (amido perylene derivative), diamine group
Figure BDA0002393658560001401
(diaminochrysene), pyrenediamine (diaminopyrenes) or a divalent iridium organometallic compound having a picolinoyl ligand, but is not limited thereto.
By matching with the host materials of the various light-emitting layers, the OLED can emit red light, green light or blue light.
Preferably, the OLED includes an electron blocking layer formed between the hole transport layer and the light emitting layer to prevent electrons from moving from the light emitting layer to the hole transport layer, and the electron blocking layer may be formed of 9,9'- (1,1' -biphenyl) -4,4'-diylbis-9H-carbazole (9,9' - (1,1'-biphenyl) -4,4' -diylbis-9H-carbazole, CBP) or 4,4',4 ″ -tris (N-carbazolyl) triphenylamine (4,4',4 ″ -tri (N-carbazolyl) -triphenylamine, TCTA), but is not limited thereto.
When the OLED device is provided with the hole blocking layer and/or the electron blocking layer, the OLED device has higher light emitting efficiency than a conventional OLED device.
The electron injection layer may be made of an electron injection material such as 8-oxonaphthalen-1-yl lithium ((8-oxonaphthalene-1-yl) lithium (ii)), but is not limited thereto.
The first electrode may be an indium-tin oxide electrode (ito electrode), but is not limited thereto.
The work function (work function) of the second electrode is lower than the work function of the first electrode. Thus, the second electrode may be, but is not limited to, an aluminum electrode, an indium electrode, or a magnesium electrode.
Other objects, effects and technical features of the present invention will be described in more detail with reference to the drawings, examples and comparative examples.
Drawings
Fig. 1 is a side view of a conventional OLED.
Fig. 2 is a side view of an OLED with a single layer ETL.
Fig. 3 is a side view of an OLED with a dual layer ETL.
Description of reference numerals:
1-an OLED device; 11-a substrate; 12-an anode; 13-hole injection layer; 14-a hole transport layer; 141-a first hole transport layer; 142-a second hole transport layer; 15-a light-emitting layer; 16-an electron transport layer; 161-a first electron transport layer; 162-a second electron transport layer; 17-an electron injection layer; 18-cathode.
Detailed Description
Several examples are listed below as examples to illustrate embodiments of the composition for an organic electronic device of the present invention and an organic electronic device using the same, so as to highlight the difference of the present invention compared to the prior art; those skilled in the art can readily appreciate from the disclosure of the present invention that the advantages and utilities of the present invention may be realized and attained without departing from the spirit and scope of the present invention.
Synthesis of intermediate an (intermediate an)
The intermediate An is useful in the preparation of a novel compound, and can be synthesized by the following procedure.
Synthesis of Intermediate An-1(Intermediate An-1)
In step 1(step 1), intermediate An-1 can be synthesized by synthetic mechanism A1, and can be used to synthetically produce intermediates A1 through A8.
Figure BDA0002393658560001411
Synthesis mechanism A1
In the synthetic mechanism A1, A may be an oxygen atom or a sulfur atom, Y1To Y3Each may be independently selected from the group consisting of: hydrogen atom, deuterium atom, alkyl group having 1 to 12 carbon atoms and aryl group having 6 to 30 carbon atoms in the ring, Y1To Y3The same or different from each other.
Synthesis of intermediate A1-1
Taking intermediate A1-1 as An example of synthetic intermediate An-1, intermediate A1-1 can be synthesized by the following synthetic mechanism A1-1.
Figure BDA0002393658560001421
Synthesis scheme A1-1
1.0 equivalent of 1-bromo-4-iododibenzofuran (1-bromo-4-iododibenzofuran), 1.0 equivalent of 1-dibenzofuranboronic acid (1-dibenzofuranboronic acid), 0.005 equivalent of tris (dibenzylideneacetone) dipalladium, Pd2(dba)3]And 0.02 equivalent of triphenylphosphine (PPh)3) Placing in a mixed solution of 0.5M dimethyl ether (DME) and 2.0M sodium carbonate aqueous solution, heating the mixed solution to 85 ℃ in a nitrogen environment, continuously stirring for 12-16 hours, cooling to room temperature after the reaction is finished, and filtering to separate precipitate generated in the reactionThen, it was recrystallized from toluene (tolumen) to obtain a white solid product with a yield of 77.4%.
The white solid product was intermediate A1-1 as determined by field desorption mass spectroscopy (FD-MS) analysis. FD-MS analysis results: c24H13BrO2Theoretical value 412.01, and detection value 412.01.
Synthesis of intermediates A2-1 to A8-1
Intermediates a2-1 to A8-2 are also useful for preparing a novel compound, and each can be synthesized by synthesis step 1, which is similar to intermediate a1-1, with the difference that different starting materials are used in the synthesis steps of intermediates a2-1 to A8-1, replacing reactant a1 with reactants a2 to A8, respectively, as starting materials. The results of the analysis of each of intermediates A1-1 to A8-1 are shown in Table 1.
Table 1: the chemical structures and CAS No. of the reactants An used for the synthesis of intermediates A1-1 to A8-1 and the chemical structures, yields, molecular formulae and masses obtained by FD-MS analysis of intermediates A1-1 to A8-1.
Figure BDA0002393658560001422
Figure BDA0002393658560001431
Modification of intermediates A1-1 to A8-1
In addition to intermediates A1-1 to A8-1, the skilled worker may replace the starting materials in the synthesis scheme A1-1, for example by choosing a different Y as described above1To Y3As starting materials for the substituents, or by selecting L as described above for different choices1And L2As starting materials, other intermediates were synthesized by a synthetic route similar to that of the synthetic mechanism A1-1.
By way of example, the remaining reactants that may be suitable as starting materials may be, but are not limited to, the following:
Figure BDA0002393658560001432
Figure BDA0002393658560001441
synthesis of intermediate An
In step 2(step 2), intermediate An can be synthesized by the synthesis mechanism a 2.
Figure BDA0002393658560001442
Synthesis mechanism A2
In the synthetic mechanism A2, A may be an oxygen atom or a sulfur atom, Y1To Y3Each may be independently selected from the group consisting of: hydrogen atom, deuterium atom, alkyl group having 1 to 12 carbon atoms and aryl group having 6 to 30 carbon atoms in the ring, Y1To Y3The same or different from each other.
Synthesis of intermediate A1
Taking intermediate A1 as An example of synthetic intermediate An, intermediate A1 can be synthesized by the following synthetic mechanism A2-1.
Figure BDA0002393658560001443
Synthesis scheme A2-1
1.0 equivalent of intermediate A1-1, 1.20 equivalents of pinacol diboron, 0.025 equivalents of [1,1-bis (diphenylphosphino) ferrocene ] were combined]Palladium dichloride [1,1-bis (diphenylphosphino) -ferrocene dichloropalladium (II), PdCl2(dppf)]And 3.0 equivalents of potassium acetate (KOAc) in 0.5M 1,4-dioxane (1,4-dioxane), followed by degassing with nitrogen and heating to about 90 ℃ for 16 hours, cooling to room temperature after completion of the reaction, followed by filtration to separate the precipitate produced by the reaction to obtain a crude product, which is then purified by distillation in a volume ratio of 1: 1 hexane and dichloromethane as eluent, purifying by column chromatography (columnhromatagraph), collecting the eluent, concentrating under reduced pressure, and adding hexaneCrystallization gave the product as a white solid in 89.0% yield.
The white solid product was intermediate a1, as determined by FD-MS analysis. FD-MS analysis results: c30H25BO4Theoretical value 460.18, and detection value 460.18.
Synthesis of intermediates A2 to A8
Intermediates a2 to A8 are also useful for preparing a novel compound, and each can be synthesized by synthesis step 2, which is similar to intermediate a1, with the difference that the synthesis steps for intermediates a2 to A8 use different starting materials, starting from reactants a2-1 to A8-1, respectively, instead of reactant a 1-1. The results of the analysis of each of intermediates a1 to A8 are listed in table 2.
Table 2: chemical structural formulae, yields, molecular formulae and masses of intermediates A1 to A8 were analyzed by FD-MS.
Figure BDA0002393658560001451
Figure BDA0002393658560001461
In addition to the above preparation methods, the intermediate An useful for preparing a novel compound can also be synthesized by the following steps.
Synthesis of intermediate An-1
In step 1 '(step 1'), intermediate An-1 can be synthesized by synthetic mechanism A3 and can be used to synthetically prepare intermediates A9 through A16.
Figure BDA0002393658560001462
Synthesis mechanism A3
In the synthetic mechanism A3, A may be an oxygen atom or a sulfur atom, Y1To Y3Each may be independently selected from the group consisting of: hydrogen atom, deuterium atom, alkyl group having 1 to 12 carbon atoms and aryl group having 6 to 30 carbon atoms in the ring, Y1To Y3The same or different from each other.
Synthesis of intermediate A9-1
Taking intermediate A9-1 as An example of synthetic intermediate An-1, intermediate A9-1 can be synthesized by the following synthetic mechanism A3-1.
Figure BDA0002393658560001463
Synthesis scheme A3-1
1.0 equivalent of 1-bromo-4-iododibenzofuran (1-bromo-4-iododibenzofuran), 1.0 equivalent of 1-dibenzofuranboronic acid (1-dibenzofuranboronic acid), 0.005 equivalent of tris (dibenzylideneacetone) dipalladium, Pd2(dba)3]And 0.02 equivalent of triphenylphosphine (PPh)3) Placing in a mixed solution of 0.5M dimethyl ether (DME) and 2.0M aqueous sodium carbonate solution, and following the same preparative procedure as synthetic mechanism A1-1, white solid product was obtained with a yield of 69.2%
FD-MS analysis confirmed that the white solid product was intermediate A9-1. FD-MS analysis results: c24H15NO2Theoretical value 349.11, and detection value 349.11.
Synthesis of intermediates A10-1 to A16-1
Intermediates a10-1 to a16-2 are also useful for preparing a novel compound, and each can be synthesized by a synthesis step 1' similar to intermediate a9-1, with the difference that different starting materials are used in the synthesis steps of intermediates a10-1 to a16-1, replacing reactant a1 with reactants a2 to A8, respectively, as starting materials. The results of the analysis of each of intermediates A9-1 to A16-1 are shown in Table 3.
Table 3: the chemical structure of reactant An used for the synthesis of intermediates A9-1 to A16-1 and the chemical structure, yield, molecular formula and mass analyzed by FD-MS of intermediates A9-1 to A16-1.
Figure BDA0002393658560001471
Figure BDA0002393658560001481
Modification of intermediates A9-1 to A16-1
In addition to intermediates A9-1 to A16-1, the skilled worker may replace the starting materials in the synthesis scheme A3-1, for example by choosing a different Y as described above1To Y3As starting materials for the substituents, or by selecting L as described above for different choices1And L2As starting materials, other intermediates were synthesized by a synthetic route similar to that of the synthetic mechanism A3-1.
By way of example, the remaining reactants that may be suitable as starting materials may be, but are not limited to, the following:
Figure BDA0002393658560001482
synthesis of intermediate An
In step 2 '-1 (step 2' -1) and step 2 '-2 (step 2' -2), the intermediate An can be synthesized by the synthesis mechanism A4.
Figure BDA0002393658560001491
Synthesis mechanism A4
In the synthetic mechanism A4, A may be an oxygen atom or a sulfur atom, Y1To Y3Each may be independently selected from the group consisting of: hydrogen atom, deuterium atom, alkyl group having 1 to 12 carbon atoms and aryl group having 6 to 30 carbon atoms in the ring, Y1To Y3The same or different from each other.
Synthesis of intermediate A9
Taking intermediate A9 as An example of synthetic intermediate An, intermediate A9 can be synthesized by the following synthetic mechanism A4-1.
Figure BDA0002393658560001492
Synthesis scheme A4-1
1.0 equivalent of intermediate A9-1 was added to a mixture of 3.0 equivalents of p-Toluenesulfonic acid hydrate (p-Toluenesulfonic acid. H)2O,p-TsOH·H2O) and 0.5M acetonitrile (CH)3CN), followed by cooling the mixed solution after the reaction to 10 c, followed by adding 2.0 equivalents of sodium nitrite (NaNO)2) After slowly adding the mixed solution of potassium iodide (KI) and 2.5 equivalents to the cooled mixed solution and stirring for reaction for 1 hour, raising the temperature to 20 ℃ and stirring for reaction for about 16 hours, then adjusting the pH to about 9 to 10 with a saturated sodium bicarbonate solution, then filtering or extracting the precipitate generated by the reaction with dichloromethane (dichloromethane), and then adding the solution to the cooled mixed solution in a volume ratio of 3: hexane and dichloromethane of 1 as eluents, and purified by flash chromatography (flash chromatography) to obtain a solid crude product.
1.0 equivalent of the above-mentioned primary product, 1.2 equivalents of pinacol diboron and 0.025 equivalents of [1,1-bis (diphenylphosphino) ferrocene ] were mixed]Palladium dichloride [1,1-bis (diphenylphosphino) -ferrocene dichloropalladium (II), PdCl2(dppf)]And 3.0 equivalents of potassium acetate in 0.5M of 1,4-dioxane (1,4-dioxane), followed by degassing with nitrogen and heating to about 90 ℃ for 16 hours, followed by the same preparative procedure as synthetic scheme A2-1 to give the product as a white solid with a yield of 55.6%.
The white solid product was intermediate A9, as determined by FD-MS analysis. FD-MS analysis results: c30H25BO4Theoretical value 460.18, and detection value 460.18.
Synthesis of intermediates A10 to A16
Intermediates a10 to a16 are also useful for preparing a novel compound, and each can be synthesized by steps 2 '-1 and 2' -2 of a synthesis similar to intermediate a9, with the difference that the steps of synthesis of intermediates a10 to a16 use different starting materials, starting materials from reactants a10-1 to a16-1, respectively, instead of reactant a 9-1. The results of the analysis of each of intermediates a9 to a16 are listed in table 4.
In Table 4, the yields of intermediates A9 to A16 were calculated by multiplying the yield of step 2 '-1 (about 65.6% to 71.4%) by the yield of step 2' -2 (about 88.6% to 93.5%) in synthetic scheme A4-1.
Table 4: chemical structural formulae, yields, molecular formulae and masses of intermediates A9 to A16 were analyzed by FD-MS.
Figure BDA0002393658560001501
Figure BDA0002393658560001511
Modification of intermediates A1 to A16
In addition to the synthetic routes described previously, modifications of intermediates a1 to a16 can also be achieved by the synthetic routes outlined below.
Figure BDA0002393658560001512
Synthesis mechanism A5
In the synthetic mechanism A5, A may be an oxygen atom or a sulfur atom, Y1To Y3Each may be independently selected from the group consisting of: hydrogen atom, deuterium atom, alkyl group having 1 to 12 carbon atoms and aryl group having 6 to 30 carbon atoms in the ring, Y1To Y3The same or different from each other.
To describe the reaction pathway of the aforementioned synthetic mechanism a5 in more detail, specific examples of the following synthetic intermediates are listed for further illustration.
Figure BDA0002393658560001521
50 g of (1- (4-dibenzofuran) -4-iododibenzofuran) (1- (dibenzofuran-4-yl) -4-iododibenzofuran), 1.05 equivalents of 4-chlorophenylboronic acid (CAS No.1679-18-1), 0.01 equivalents of palladium acetate (palladium (II) acetate, Pd (OAc)2) 0.04 equivalent of 2- (dicyclohexylphosphino) biphenyl (2- (dicyclohexylphosphino) biphenyl, PCy2(2-biPh)) and 2.0 equivalents of potassium carbonate were mixed in a mixed solution of toluene (340 ml), ethanol (34 ml) and water (72 ml), heated to 80 ℃ and stirred under reflux under a nitrogen atmosphere for 16 hours, and after the reaction was completed and cooled to room temperature, the mixed solution was extracted and the crude product was collected from the organic layer, dried over magnesium sulfate, separated by filtration and concentrated to dryness, and then purified by silica gel column chromatography to obtain 43 g of a white solid product with a yield of 89%.
The result of FD-MS analysis of the white solid product: c30H17ClO2Theoretical molecular weight is 444.91, and detectable molecular weight is 444.91.
Synthesis of novel compounds
It is mentioned that different intermediates, namely intermediate An, can react with different reactants Bn and give novel compounds (tethered compounds) whose synthetic route is summarized in scheme I. In the synthesis scheme I, "reactant Bn" is selected from any one of the group comprising reactants B1-B9 and B9' in table 5; "intermediate An" is selected from any one of the group comprising intermediates a1 to a16 in table 4 or a similar one, but is not limited thereto.
Figure BDA0002393658560001522
Mechanism of Synthesis I
Table 5: chemical structures and CAS numbers of reactants B1-B9 and B9'.
Figure BDA0002393658560001523
Figure BDA0002393658560001531
Mechanism of Synthesis I
In Synthesis scheme I, 1.0 equivalent of intermediate an (Intermediate an), 1.0 equivalent of reactant Bn (reactant Bn), 0.01 equivalent of tris (dibenzylideneacetone) dipalladium [ tris (dibenzylideneacetone) ]tone)dipalladium,Pd2(dba)3]And 0.02 equivalent of tricyclohexylphosphinothiofluoroborate (PCy)3*HBF4) Placing the mixture in a volume ratio of 1,4-dioxane to toluene of 2: 1 and 2.0M aqueous solution of sodium carbonate, and refluxing for about 12 to 16 hours, cooling to room temperature after the reaction is completed, filtering and separating the precipitate produced by the reaction to obtain an initial product, and then recrystallizing with o-dichlorobenzene (otho-dichlorobenzene) to obtain a white solid product, which is the novel compound of the present invention.
The novel compounds of the invention can also be obtained by summarizing the reaction pathways in scheme II. In the synthesis scheme II, "reactant Bn" is selected from any one of the group comprising reactants B10-B11 in table 6; "intermediate An" is selected from any one of the group of the aforementioned intermediates a 1-a 16 or a similar one, but is not limited thereto.
Figure BDA0002393658560001532
Mechanism of Synthesis II
Table 6: chemical structural formulas and CAS numbers of reactants B10-B11.
Figure BDA0002393658560001533
Mechanism of Synthesis II
In synthetic scheme II, 1.0 equivalent of intermediate an (Intermediate an), 1.0 equivalent of reactant Bn (reactant Bn), 0.01 equivalent of palladium acetate (palladium (II) acetate, Pd (OAc)2) And 0.02 equivalent of 2- (dicyclohexylphosphino) biphenyl (2- (dicyclohexylphosphino) biphenyl, PCy2(2-biPhenyl)) was placed in a volume ratio of toluene to ethanol of 1: 0.1 and 2.0M aqueous solution of sodium carbonate, and refluxing for about 8 to 12 hours, cooling to room temperature after the reaction is completed, filtering and separating the precipitate produced by the reaction to obtain an initial product, and then recrystallizing the initial product with o-dichlorobenzene to obtain a white solid product, which is the novel compound of the present invention.
Intermediates An and reactants Bn used to synthesize the novel compounds are listed in table 7. Each of the novel compounds 1 to 20 is produced by hydrogen nuclear magnetic resonance spectroscopy (1H-NMR) and FD-MS analysis, the chemical structural formulas, yields, molecular formulas and masses of compounds 1 to 20 are also listed in table 7; the results of the hydrogen nuclear resonance spectroscopy analysis of the compounds 1 to 5 and 7 to 20 are shown in Table 8.
Table 7: intermediates An and reactants Bn used in the synthesis of compounds 1 to 20 and the chemical structural formulae, yields, molecular formulae and masses obtained by FD-MS analysis of compounds 1 to 20.
Figure BDA0002393658560001541
Figure BDA0002393658560001551
Figure BDA0002393658560001561
Figure BDA0002393658560001571
Figure BDA0002393658560001581
Figure BDA0002393658560001591
Figure BDA0002393658560001601
Modification of novel compounds
In addition to the aforementioned compounds 1 to 20, one skilled in the art can substitute different intermediate a (i.e., the aforementioned intermediate An or a similar one) and different reactant Bn or a similar one, and synthesize other novel compounds in a synthetic route similar to that of synthetic scheme I or synthetic scheme II.
Preparation of OLED devices
Will be coated with a thickness of
Figure BDA0002393658560001602
The glass substrate of the ITO layer (hereinafter referred to as an ITO substrate) of (1) was placed in distilled water (obtained by filtering twice with a filter of Millipore Co.) containing a detergent (trade name: Fischer Co.) and was subjected to ultrasonic oscillation for 30 minutes; replacing distilled water, then using ultrasonic wave to vibrate for 10 minutes to clean the ITO substrate, and repeating the cleaning step once; after cleaning, the glass substrate is cleaned by ultrasonic vibration of isopropanol, acetone and methanol and dried; then, the glass substrate is placed in a plasma surface cleaning machine, and is cleaned for 5 minutes by oxygen plasma, and then the cleaned glass substrate is placed in a vacuum evaporation machine.
Thereafter, the vacuum degree of the vacuum evaporator was maintained at 1 × 10-6torr to 3x10-7torr, and various organic materials and metal materials were sequentially deposited on the ITO substrate, and the OLED devices of examples 1 to 51 and comparative examples 1 to 12 were obtained. Herein, a Hole Injection Layer (HIL), a first hole transport layer (HTL-1), a second hole transport layer (HTL-2), a blue/green/red light emitting layer (BEL/GEL/REL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), and a cathode (Cthd) are sequentially deposited on the ITO substrate.
Wherein HI and HI-D are materials for forming HIL; HT1 is a material used to form HTL-1; B-HT2/G-HT2/R-HT2 are materials used to form the HTL-2 of the blue/green/red OLED, respectively; the novel compounds described herein are used to form the ETL of the examples, ET1 and ET2 are the materials used to form the ETL of the comparative examples; liq is a material used to form ETLs and EILs; BH/GH/RH is the host material (BH/GH/RH) used to form BEL/GEL/REL, respectively, and BD/GD/RD is the dopant for BEL/GEL/REL, respectively.
The largest difference between the OLED devices of the examples and the OLED devices of the comparative examples was that the electron transport material of the ETL in the OLED device of the comparative example was made of ET1 and ET2 listed in table 9, while the electron transport material of the ETL in the OLED device of the examples was made of the compound of the present invention. Specifically, the electron transport materials used in examples 1 to 51 are listed in table 7.
Table 9: chemical structures of commercial materials, ET1 and ET2, used in OLED devices.
Figure BDA0002393658560001611
Single-layer ETL OLED device
In the OLED device of the single-layer ETL, various organic materials and metal materials were sequentially deposited on the ITO substrate as well, and the OLED devices of examples 1 to 32 and comparative examples 1 to 6 were obtained. As shown in fig. 2, the OLED device 1 sequentially includes a substrate 11, an anode 12, a hole injection layer 13, a hole transport layer 14 including a first hole transport layer 141 and a second hole transport layer 142, a light emitting layer 15, an electron transport layer 16, an electron injection layer 17, and a cathode 18.
Preparation of blue-light OLED device
The blue OLED device included a plurality of organic layers deposited on the ITO substrate in the order in table 10, and the materials and thicknesses of the respective organic layers are also listed in table 10.
Table 10: the coating order, name, materials and thickness of the various organic layers in a blue OLED device.
Figure BDA0002393658560001621
Preparation of Green light OLED device
The green OLED device included a plurality of organic layers deposited on the ITO substrate in the order in table 11, and the materials and thicknesses of the respective organic layers are also listed in table 11.
Table 11: the order of application, materials and thicknesses of the various organic layers in the green OLED device.
Figure BDA0002393658560001622
Preparation of Red-light OLED device
The red OLED device included a plurality of organic layers deposited on the ITO substrate in the order in table 12, and the material and thickness of each organic layer are also listed in table 12.
Table 12: the coating sequence, materials and thicknesses of the various organic layers in a red OLED device.
Figure BDA0002393658560001631
Performance of OLED devices
In order to evaluate the performance of the OLED device, the red, green and blue OLED devices were connected to a power supply (trademark: Keithley; model: 2400), respectively, and measured with a luminance meter of PR650, and the measured chromaticity was shown as chromaticity coordinates (x, y) formulated by the Commission Internationale de L' Eclairage 1931, CIE.
Life test
The lifetime test was performed according to the OLED lifetime test system (Chroma model 58131). Lifetime tests were performed for the blue, green and red OLED devices, respectively, according to the following conditions.
The lifetime (T85) was defined as the time required for the OLED device to fall to 85% brightness relative to the initial brightness for a blue OLED device tested at 2000 nits brightness and the test results are set forth in table 13.
The lifetime (T95) was defined as the time required for the OLED device to fall to 95% brightness relative to the initial brightness for the green OLED device tested at 7000 nits and the test results are set forth in table 14.
The lifetime (T90) was defined as the time required for the OLED device to fall to 90% brightness relative to the initial brightness for a red OLED device tested at 6000 nits and the test results are set forth in table 15.
The ETL materials, CIE chromaticities and measured lifetimes used for examples 1 to 32 and comparative examples 1 to 6 are listed in tables 13, 14 and 15.
Table 13: number of blue OLED devices, ETL materials, CIE (x, y) chromaticity and lifetime test results.
Figure BDA0002393658560001632
Figure BDA0002393658560001641
Table 14: number of green OLED devices, ETL materials, chromaticity CIE (x, y), and lifetime test results.
Figure BDA0002393658560001642
Table 15: number of red OLED devices, ETL materials, CIE (x, y) chromaticity and lifetime test results.
Figure BDA0002393658560001643
According to the experimental results shown in tables 13 to 15, the service life of the blue, green or red OLED device having a single electron transport layer can be effectively prolonged when the novel compound of the present invention is used as an electron transport material in an electron transport layer, compared to when ET1 and ET2 are used as electron transport materials in an electron transport layer.
Double-layer ETL OLED device
The OLED device of the double-layer ETL is quite similar in structure to the OLED of the aforementioned single-layer ETL, and various organic materials and metal materials are sequentially deposited on the ITO substrate as well, and the OLED devices of examples 33 to 51 and comparative examples 7 to 12 are obtained. Here, referring to fig. 3, the OLED device 1 sequentially includes a substrate 11, an anode 12, a hole injection layer 13, a hole transport layer 14 including a first hole transport layer 141 and a second hole transport layer 142, a light emitting layer 15, an electron transport layer 16 including a first electron transport layer (ETL-1) 161 and a second electron transport layer (ETL-1) 162, an electron injection layer 17, and a cathode 18.
Preparation of blue-light OLED device
The blue OLED device included a plurality of organic layers deposited on the ITO substrate in the order in table 16, and the materials and thicknesses of the respective organic layers are also listed in table 16.
Table 16: the coating order, name, materials and thickness of the various organic layers in a blue OLED device.
Figure BDA0002393658560001651
Preparation of Green light OLED device
The green OLED device included a plurality of organic layers deposited on the ITO substrate in the order in table 17, and the materials and thicknesses of the respective organic layers are also listed in table 17.
Table 17: the order of application, materials and thicknesses of the various organic layers in the green OLED device.
Figure BDA0002393658560001652
Figure BDA0002393658560001661
Preparation of Red-light OLED device
The red OLED device included a plurality of organic layers deposited on the ITO substrate in the order in table 18, and the material and thickness of each organic layer are also listed in table 18.
Table 18: the coating sequence, materials and thicknesses of the various organic layers in a red OLED device.
Figure BDA0002393658560001662
Performance of OLED devices
The performance of the OLED device with the double-layer ETL was evaluated in the same manner as the single-layer ETL, using the same equipment, conditions and procedures.
Life test
The ETL-2 materials, CIE chromaticity and measured lifetime used in examples 33 to 51 and comparative examples 7 to 12 are set forth in tables 19, 20 and 21.
Table 19: number of blue OLED devices, ETL-2 material, chromaticity CIE (x, y), and lifetime test results.
Figure BDA0002393658560001663
Figure BDA0002393658560001671
Table 20: number of green OLED devices, ETL-2 material, chromaticity CIE (x, y), and lifetime test results.
Figure BDA0002393658560001672
Table 21: number of red OLED devices, ETL-2 material, chromaticity CIE (x, y), and lifetime test results.
Figure BDA0002393658560001673
According to the experimental results shown in tables 19 to 21, the service life of the blue, green or red OLED device having a two-layer electron transport layer can be effectively prolonged when the novel compound of the present invention is used as the electron transport material in the second electron transport layer, compared to when ET1 and ET2 are used as the electron transport material in the second electron transport layer.
Drive voltage test
In addition to testing the lifetime of the OLED device, the driving voltage of the OLED device with the double-layer ETL was further evaluated. The ETL-2 material, CIE chromaticity, and measured driving voltage used for examples 33, 36, 40 to 42, 45 to 47, and 51 and comparative examples 7 to 12 are listed in table 22.
Table 22: the numbers of blue, green and red OLED devices, ETL-2 materials, CIE (x, y) chromaticity and driving voltage test results.
Figure BDA0002393658560001681
As shown in the experimental results of table 22, compared to the use of ET1 and ET2 as the electron transport material in the second electron transport layer, the novel compounds of the present invention can also have the effect of reducing the driving voltage of the blue, green, or red OLED device having a two-layer electron transport layer when used as the electron transport material in the second electron transport layer.
In summary, no matter for the blue, green or red OLED devices with single-layer or double-layer electron transport layers, compared with the electron transport layer materials used conventionally, the novel compound of the present invention can achieve the effect of effectively prolonging the service life of the blue, green or red OLED devices when used as the electron transport material in the electron transport layer; moreover, for a blue, green or red OLED device with a double-layer electron transport layer, when the novel compound of the present invention is used as an electron transport material in the electron transport layer, the effect of reducing the driving voltage of the blue, green or red OLED device with a double-layer electron transport layer is further achieved.
The above-described embodiments are merely examples for illustrating the present invention and do not limit the scope of the claims of the present invention in any way, and those skilled in the art can adjust the number, position or arrangement of the substituents according to the spirit of the present invention. The scope of the invention is not to be limited to the specific embodiments described above, but is to be accorded the full scope consistent with the claims.

Claims (16)

1. A novel compound represented by the following formula (I):
Figure FDA0002393658550000011
wherein a1, a2, b and c represent connecting positions, b is connected with any one of a1 or a2, c is connected with the other one of a1 or a 2;
wherein G is1B is
Figure FDA0002393658550000012
Wherein G is2Selected from the group consisting of:
Figure FDA0002393658550000013
wherein Z is1And Z2Each independently selected from the group consisting of: a substituted aryl group having 6 to 60 carbon atoms in the ring, an unsubstituted aryl group having 6 to 60 carbon atoms in the ring, a substituted heteroaryl group having 3 to 60 carbon atoms in the ring, and an unsubstituted heteroaryl group having 3 to 60 carbon atoms in the ring;
wherein m1 to m4 are each independently 0 or 1, and m1 to m4 are the same as or different from each other;
wherein L is1To L4Each independently an arylene group having 6 to 60 carbon atoms in the ring, and L1To L4Are the same or different from each other;
wherein, Y1To Y3Each independently selected from the group consisting of: hydrogen atom, deuterium atom, alkyl group having 1 to 12 carbon atoms and aryl group having 6 to 30 carbon atoms in the ring, and Y1To Y3The same or different from each other.
2. The compound of claim 1, wherein the compound is represented by any one of formulae (I-I) to (I-XVI):
Figure FDA0002393658550000021
Figure FDA0002393658550000031
3. the compound of claim 1, wherein Z is1And Z2Each independently selected from the group consisting of:
Figure FDA0002393658550000032
Figure FDA0002393658550000041
wherein R is1To R7Each independently selected from the group consisting of: a hydrogen atom, a deuterium atom, a halogen group, a cyano group, a nitro group, a trifluoromethyl group, an unsubstituted alkyl group having 1 to 12 carbon atoms, an unsubstituted alkenyl group having 2 to 12 carbon atoms, an unsubstituted alkynyl group having 2 to 12 carbon atoms, an unsubstituted aryl group having 6 to 30 carbon atoms in the ring, an unsubstituted heteroaryl group having 3 to 30 carbon atoms in the ring, and a heteroaryl group having 3 to 30 carbon atoms in the ring; wherein the substituents are selected from the group consisting of: deuterium atom, halogen group, cyano group, nitro group, and trifluoromethyl group;
wherein m is an integer of 1 to 4, n is an integer of 1 to 3, and o is 1 or 2.
4. The compound of claim 1, wherein Z is1Selected from the group consisting of:
Figure FDA0002393658550000042
Z2selected from the group consisting of:
Figure FDA0002393658550000043
Figure FDA0002393658550000051
wherein R is1To R7Each independently selected from the group consisting of: a hydrogen atom, a deuterium atom, a halogen group, a cyano group, a nitro group, a trifluoromethyl group, an unsubstituted alkyl group having 1 to 12 carbon atoms, an unsubstituted alkenyl group having 2 to 12 carbon atoms, an unsubstituted alkynyl group having 2 to 12 carbon atoms, an unsubstituted aryl group having 6 to 30 carbon atoms in the ring, an unsubstituted heteroaryl group having 3 to 30 carbon atoms in the ring, and a heteroaryl group having 3 to 30 carbon atoms in the ring; wherein the substituents are selected from the group consisting of: deuterium atom, halogen group, cyano group, nitro group, and trifluoromethyl group;
wherein m is an integer of 1 to 4, n is an integer of 1 to 3, and o is 1 or 2.
5. The compound of claim 1, wherein Z is1And Z2Each independently selected from the group consisting of:
Figure FDA0002393658550000061
wherein R is1To R7Each independently selected from the group consisting of: hydrogen atom, deuterium atom, halogen group, cyano group, nitro group, trifluoromethyl group, unsubstituted alkyl group having 1 to 12 carbon atoms, alkyl group having 1 to 12 carbon atoms and being substituted with a substituent, unsubstituted alkenyl group having 2 to 12 carbon atoms, alkenyl group having 2 to 12 carbon atoms and being substituted with a substituent, alkynyl group having 2 to 12 carbon atoms and being substituted with a substituentAn alkynyl group having 2 to 12 carbon atoms, an unsubstituted aryl group having 6 to 30 carbon atoms in the ring, an aryl group having 6 to 30 carbon atoms in the ring and substituted with a substituent, an unsubstituted heteroaryl group having 3 to 30 carbon atoms in the ring and a heteroaryl group having 3 to 30 carbon atoms in the ring and substituted with a substituent; wherein the substituents are selected from the group consisting of: deuterium atom, halogen group, cyano group, nitro group, and trifluoromethyl group;
wherein m is an integer of 1 to 4, n is an integer of 1 to 3, and o is 1 or 2.
6. A compound of claim 4, wherein R is1To R7Each independently selected from the group consisting of: hydrogen atom, deuterium atom, halogen group, cyano group, nitro group, trifluoromethyl group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, phenyl group, naphthyl group, biphenyl group, terphenyl group, and trifluoromethylphenyl group.
7. The compound of claim 1, wherein Z is1And Z2Each independently selected from the group consisting of:
Figure FDA0002393658550000071
Figure FDA0002393658550000081
8. the compound of claim 1, wherein L is1To L4Each arylene group having 6 to 60 carbon atoms in the ring is independently selected from the group consisting of:
Figure FDA0002393658550000082
wherein m is an integer of 1 to 4, n is an integer of 1 to 3, o is 1 or 2;
wherein,X1and X2Each independently selected from the group consisting of: a hydrogen atom, a deuterium atom, a halogen group, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 30 carbon atoms in the ring, a heteroaryl group having 3 to 30 carbon atoms in the ring, and an aryloxy group having 6 to 30 carbon atoms in the ring.
9. The compound of claim 1, wherein Y is1To Y3Each independently selected from the group consisting of: hydrogen atom, deuterium atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, phenyl group, biphenyl group, and naphthyl group.
10. The compound of claim 1, wherein G is2Selected from the group consisting of:
Figure FDA0002393658550000091
Figure FDA0002393658550000101
Figure FDA0002393658550000111
Figure FDA0002393658550000121
Figure FDA0002393658550000131
Figure FDA0002393658550000141
Figure FDA0002393658550000151
Figure FDA0002393658550000161
Figure FDA0002393658550000171
Figure FDA0002393658550000181
Figure FDA0002393658550000191
Figure FDA0002393658550000201
Figure FDA0002393658550000211
Figure FDA0002393658550000221
Figure FDA0002393658550000231
Figure FDA0002393658550000241
Figure FDA0002393658550000251
11. the compound of claim 1, wherein the compound is selected from the group consisting of:
Figure FDA0002393658550000252
Figure FDA0002393658550000261
12. an organic electronic device comprising a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode, wherein the organic layer comprises the compound of any one of claims 1 to 11.
13. The organic electronic device according to claim 12 wherein the organic electronic device is an organic light emitting diode.
14. The organic electronic device of claim 13, wherein the organic light emitting diode comprises:
a hole injection layer formed on the first electrode;
a hole transport layer formed on the hole injection layer;
a light emitting layer formed on the hole transport layer;
a first electron transport layer formed on the light emitting layer, wherein the first electron transport layer is the organic layer; and
an electron injection layer formed between the first electron transport layer and the second electrode.
15. The organic electronic device according to claim 14, wherein the organic light emitting diode comprises a second electron transport layer formed between the light emitting layer and the first electron transport layer.
16. The organic electronic device according to claim 14, wherein the organic light emitting diode comprises a second electron transport layer formed between the electron injection layer and the first electron transport layer.
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